Acidic esters of oxypropylated pentamines



Patented May 25, 1954 UNi'iED 'STATES ATENT OFFICE ACIDIC ESTERS F OXYPROPYLATED PENTAMINES Melvin De Groote, University City,

to Petrolite Corporation ware Mo., assignor a. corporation of Dela- No Drawing. Application May 14, 1951,

Serial No. 226,309

Claims.

chemical products, pounds or compositions, as Well as the products, compounds, or compositions themselves.

Complementary to the above aspect of the invention herein disclosed is my companion invention concerned with the use of these particular chemical compounds, or products, as demulsifying agents in processes or procedures particularly adapted for preventin breaking, or resolving emulsion of the water-in-oil type, and particularly petroleum emulsions. See my co-pending application, Serial No. 226,308, filed May 14, 1951, new Patent No. 2,626,917.

lhe last aforementioned co-pending application, i. e., Serial No. 107,381, now Patent No. 2,- 552,530, describes high molal oxypropylation derivatives of monomeric polyamino compounds with the proviso that (a) the initial polyamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (1)) the initial polyamino reactant having a molecular weight of not over 1800- and at least a plurality of reactive hydrogen atoms; (0) the initial polyamino reactant must be water-soluble; (d) the oxyoropylation end product must be water-insoluble; (e) the cxypropylation end product be within the molecular weight range of 2000 to 30,000 on an average statistical basis; (f) the solubility characteristics of the oxypropylation end product in respect to water must be substantially the result of the oxypropylation step; (c) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to 70; (h) the initial polyamino reactant must represent not more than 20% by weight of the oxypropylation end product on a statistical basis; (2') the preceding provisos are based on the assumption of com plete reaction involving the propylene oxide and initial polyamino reactant; (j) the polyamino reactant must contain at least one basic nitrogen atom; and (k) the nitrogen atoms are linked by a carbon atom chain.

Furthermore, in said aforementioned co-pending application it was pointed out that such hydroxylated materials obtained by oxypropylation could be reacted with seven terminal hydroxyl radicals or the equivalent, i. e., labile hydrogen atoms susceptible to oxyalkylation.

bination of the two, particularly tetraethylenepentamine treated with one to five, six or seven or even eight moles of ethylene oxide.

The initial pent-amine must be characterized by (a) having 7 amino nitrogen atoms and preferably all being basic; (b) free from any radical having 8 or more carbon atoms in an uninterrupted group; (0) must be water-soluble; and (d) have a plurality of reactive hydrogen atoms, preferably at least 3, 4 or 5.

Needless to say, the most readily available reactant, to wit, tetraethylenepentamine has 7 reactive hydrogen atoms and this after treatment with ethylene oxide, for instance, 7 moles of ethylene ox with glycide would provide as many as 14 reactive hydrogen atoms provided the molal ratio was still the same as before, to wit, '7 moles of glycide per mole of pentamine. On the other hand, if tetraethylenepentamine were treated with an alkylating agent so as to introduce an alkyl radical such as methyl, ethyl, propyl, butyl, hexyl, heptyl, or the like, or an aryl radical such as a phenyl radical, then and in that event the number of reactive hydrogen atoms might be decreased to as few as two, three, or four and still be acceptable for the instant purpose. If an alkyl radical or an alicyclic radical, such as a cyclohexyl radical, or an alkyl-aryl radical such as a benzyl radical, were introduced the basicity of the nitrogen atom would not be materially affected. However, the introduction of a phenyl radical would, of course, markedly affect the basicity of the nitrogen atom. For obvious reasons my choice is as follows: (a) The use of tetraet-hylenepentamine rather than any substituted tetraethylenepentamine as described; (12) the use of tetraethylenepentamine after treatment with 1 to '7 moles of ethylene oxide although a modestly increased amount of ethylene oxide can be used in light of what is said hereinafter, or as (c) the use of a derivative obtained from tetraethylenepentamine after reaction with glycide, or a mixture of ethylene oxide and glycide.

Since reaction of tetraethylenepentamine with propylene oxide is invariably involved and since this oxyalkylation step was substantially the same as the use of ethylene oxide or glycide, for purpose of brevity further reference will be made to tetraethylenepentamine as illustrating the procedure regardless of what particular reactant is selected. It is not necessary to point out, or" course, that the substituted tetraethylenepentamines, i. e., those where an alkyl radical, alicyclic radical, aryl-alkyl, or aryl group has been introduced can be subjected similarly to reaction with ethylene oxide, glycide, or a combination of the two.

I also want to point out it is immaterial whether the initial oxypropylation step involves hydrogen attached to oxygen or hydrogen attached to nitrogen. The essential requirement is that it be a labile or reactive hydrogen atom. Any substituent radical present must, of course, have less than 8 uninterrupted carbon atoms in a single group.

More specifically then, the present invention is concerned with hydrophile synthetic products; said hydrophile synthetic product being the acidic fractional esters derived by reaction between (A) a polycarboxy acid and (B) high molal oxypropylation derivatives of monomeric pentamino compounds, with the proviso that (a) the initial pentamino reactant be free from any radical having at least 8 uninterrupted carbon atoms; (12) the initial pentamino reactant have a molecular weight of not over 865 and at least a plurality of reactive hydrogen atoms; (a) the initial pentamino reactant must be water-soluble; (d) the oxypropylation end product must be water-insoluble, and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2500 to 30,000 on an average statistical basis; (f) the solubility characteristics of the oxyproyplation end product in respect to water and kerosene must be substantially the result of the oxypropylation step; (g) the ratio of propylene oxide per initial reactive hydrogen atom must be within the range of 7 to '70; (h) the more than 20% by weight of the oxypropylation end product on a statistical basis; (i) the preceding provisos are based on the assumption of complete reaction involving the propylene oxide and initial pentamino reactant; (9) the nitrogen atoms are linked by an ethylene chain, and with the further proviso that the ratio of (A) to (B) be one mole of (A) for each hydroxyl radical present in (B).

What has been said previously in regard to the materials herein described and particularly for use as clemulsifiers with reference to fractional esters may be and probably is an oversimplification for reasons which are obvious on further examination. It is pointed out subsequently that prior to esterification-the alkaline catalyst can be removed by addition of hydrochloric acid. Actually the amount of hydrochloric acid added is usually sufiicient and one can deliberately employ enough acid, not only to neutralize the alkaline catalyst but also to neutralize the amino nitrogen atom or convert it into a salt. Stated an other way, a trivalent nitrogen atom is converted into a pentavalent nitrogen atom, i. e., a change involving an electrovalency indicated as follows:

HX a

wherein HX represents any strong acid or fairly strong acid such as hydrochloric acid, nitric acid, sulfuric acid, a sulphonic acid, etc. in which H represents the acidic hydrogen atom and X represents the anion. Without attempting to complicate the subsequent description further it is obvious then that one might have esters or one might convert the esters into ester salts as described. Likewise another possibility is that under certain conditions one could obtain amides. The explanation of this latter fact resides in this observation. In the case of an amide, such as acetamide, there is always a question as to whether or not oxypropylation involves both amido hydrogen atoms so as to obtain a hundred per cent yield of the dihydroxylated compound. There is some evidence to at least some degree that a monohydroxylated compound is obtained under some cir cumstances with one amido hydrogen atom remaining without change.

Another explanation which has sometimes appeared in the oxypropylation of nitrogencontaining compounds particularly such as acetamide, is that the molecule appears to decompose under conditions of analysis and unsaturation seems to appear simultaneously. One suggestion has been that one hydroxyl is lost by dehydration and that this ultimately causes a break in the molecule in such a way that two new hydroxyls are formed. This is shown after a fashion in a highly idealized manner in the following way:

initial pentamino reactant must represent not 75. In the above formulas the large X is obviously not 5 intended to signify anything except the central part of a large molecule, whereas, as far as a speculative explanation is concerned, one need only consider the terminal radicals, as shown. Such suggestion is of interest only because it may be a possible explanation of how an increase in hydroxyl value does take place which could be interpreted as a decrease in molecular weight. This matter is considered subsequently in the final paragraphs of Part 2. This same situation seems to apply on the oxypropylation of at least some polyalkylene amines and thus is of significance in the instant situation.

In the case of higher then the two hydrogen atoms on the two inter mediate nitrogen atoms. Thus four chains tend to build up and perhaps finally, if at all, the remaining two hydrogen atoms attached to the mediate nitrogen atoms, and then finally, if at all depending on conditions of oxypropylation, the two remaining terminal hyrogen atoms are attacked.

If this is the iation at the case it is purely a matter of specumoment because apparently there one has a situation somewhat comparable acylation of monoethanolamine or diethanoleither the hydrogen atom attached to the hydrogen atom attached to nitrogen.

As far as the herein described compounds are involved. By materials obtained are obviously fractional esters, for reasons which are apparent in light of what has been said and in light of what appears hereinafter.

However, in order to present the invention in its broadest aspect it had best be re-stated as with certain hydrophile synthetic products; said hydrophile synthetic products being a cogeneric mixture selected from For to the I the initial pentamino reactant must be water-soluble; (d) the oxyprcpylation end product must be water-insoluble and kerosene-soluble; (e) the oxypropylation end product be within the molecular weight range of 2500 to 30,000 on an average statistical basis;

the final proviso that the ratio of (A) to (B) present in (B).

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the specific application is described and claimed in my co-pending application, Serial No. 226, 308, filed May 14, 1951, now Patent No. 2,626,917.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile ining negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For convenience what is said hereafter will be divided into four parts:

Part 1 is concerned with the preparation of the oxypropylation derivative of tetraethylenepentamine or equivalent initial reactants;

Part 2 is concerned with the preparation of the esters from the oxypropylated derivatives;

Part 3 is concerned with the nature of the oxypropylation derivatives insofar that such co- PART 1 For a number of well knnu/"n v n any of the customarily available alkylene oxides,

i. e., ethylene oxide, propylene oxide, butylene oxide, glycide, epichlorohydrin, styrene oxide, etc. In the subsequent description of the equipment it becomes obvious thatit is adapted for oxyethylation as well as oxypropylation.

Oxypropylations are conducted under a wide variety of conditions, not only in regard to presence or absence of catalyst, and the kind of catalyst, but also in regard to the time of reaction, temperature of reaction, speed of reaction, pressure during reaction, etc. For instance, oxyalkylations can be conducted at temperatures up to approximately 200 C. with pres sures in about the same range up to about 200 pounds per square inch. They can be conducted also at temperatures approximating the point of water or slightly above, as for example 95 to 120 C. Under such circumstances the pressure will be less than 30 pounds per square inch unless some special procedure is employed as is sometimes the case, to wit, keeping an atmosphere of inert gas such as nitrogen in the vessel during the reaction. Such low-temperature-low reaction rate oxypropylations have been described very completely in U. S. Patent No. 2,448,664, to H. R. Fife, et al., dated September '7, 1948. Low temperature, low pressure oxypropylations are particularly desirable where the compound being subjected to oxypropylation contains one, two or three points of reaction only, such as monohydric alcohols, glycols and triols.

The initial reactants in the instant application contain at least 2 reactive hydrogens and for this reason there is possibly less advantage in using low temperature oxypropylation rather than high temperature oxypropylation. However, the reactions do not go too slowly and this particular procedure was used in the subsequent examples.

Since low pressure-low temperature-lowreaction-speed oxypropylations require considerable time, for instance, 1 to '7 days of 24: hours each to complete the reaction they are conducted as a rule whether on a laboratory scale, pilot plant scale, or large scale, so as to operate automatically. The prior figure of seven days applies especially to large-scale operations. I have used conventional equipment with two added automatic features: (a) which shuts oil the propylene oxide in event that the temperature gets outside a predetermined and set range, for instance, 95 to 120 0., and (1)) another solenoid valve which shuts off the propylene oxide (or for that matter ethylene oxide if it is being used) if the pressure gets beyond a predetermined range, such as 25 to 35 pounds. Otherwise, the equipment is substantially the same as is commonly employed for this purpose where the pressure of reaction is higher,

speed of reaction is higher, and time of reaction is much shorter. In such instances such automatic controls are not necessarily used.

Thus, in preparing the various examples I have found it particularly advantageous tcry equipment or pilot plant which is designed to permit continuous oxyalkylation whether it be oxypropylation or oxyethylation. With certain obvious changes the equipment can be used a mmumiqfinn involving the use of to use labora- '5 a solenoid controlled valve tinuous operation,

glycide where no presssure is involved except the vapor pressure of a solvent, if any, which may have been used as a diluent.

As previously pointed out the method of using propylene oxide is the same as ethylene oxide. This point is emphasized only for the reason that the apparatus is so designed and constructed as to use either oxide.

The oxypropylation procedure employed in the preparation of the oxyalkylated derivatives has been uniformly the same, particularly in light of the fact that a continuous automatically-controlled procedure was employed. In this procedure the autoclave was a conventional autoclave made of stainless steel and having a capacity of approximately 15 gallons and a working pressure of one thousand pounds gauge pressure. This pressure obviously is far beyond any requirement as far as propylene oxide goes unless there is a reaction of explosive violence involved due to accident. The autoclave was equipped with the conventional devices and openings, such as the variable-speed stirrer operating at speeds from R. P. M. to 500 R. P. M.; thermometer well and thermocouple for mechanical thermometer; emptying outlet, pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for introducing the alkylene oxide, such as propylene oxide or ethylene oxide, to the bottom of the autoclave; along with suitable devices for both cooling. and heating the autoclave, such as a cooling jacket, and, preferably, coils in addition thereto, with he jack t 50 arranged that it is suitable for heating with steam or cooling with water and further equipped with electrical heating devices. Such autoclaves are, of course, in essence small-scale replicas of the usual conventional autoclave used in oxyalkylation procedures. In some instances in exploratory preparations an autoclave having a smaller capacity, for instance, approximately 3 /2 liters in one case and about 1 gallons in another case, was used.

Continuous operation, or substantially conwas achieved by the use of a separate container to hold the alkylene oxide being employed, particularly propylene oxide. In conjunction with the smaller autoclaves, the container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. In some instances a larger bomb was used, to wit, one having a capacity of about one gallon. This bomb was equipped, also with an inlet for charging, and an eductor tube going to the bottom or the container so as to permit discharging cf allrylene oxide in the liquid phase to the autoclave. A bomb having a capacity of about pounds was used in connection with the l5-gallon autoclave. Other conventional equipment consists, of course, of the rupture disc, pressure gauge, sight feed glass, thermometer, connection for nitrogen for pressuring bomb, etc. The bomb Was placed on a scale during use. The connections between the bomb and the autoclave were flexible stainless steel hose or tubing so that continuous weighings could be made without breaking or making any connections. This applies also to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass protective screens, etc.

Attention is directed again to what has been said previously in regard to automatic controls which shut OK the propylene oxide in event temout of predetermined range.

With this particular arrangement practically all oxypropylations become uniform in that the C. or lower point would be 95 or possibly 98 C. Similarly, the pressure was held at approximately 30 pounds within a -pound variacompared with oxyalkylations at 200 ous reactions where within the first 5 period or two-thirds of anymined amount would react the 8-hour of course, an inherent danger and appropriate steps possibility; if need be a sample must be withdrawn and examined for unreacted propylene oxide.

temperature, for instance, at 140 to 150 C. Unreacted oxide affects determination of the acetyl or hydroxyl 0 molecular weight of pound, i. e., towards the latter stages of reaction the longer the time required to add a given amount of oxide. One possible explanation is that the molecule, being larger, the opportunity for random reaction is decreased. Inversely, the lower the molecular weight the faster the reaction takes place. For this reason, sometimes at must be taken to safeguard against this 10 kylation has a comparatively high molecular weight. However, as has been pointed out previously, operating at a low pressure and a low counterbalance scale or dial scale holding the propylene oxide bomb was so set that when the predetermined amount of propylene oxide had passed into the reaction the scale movement through a time opwere conventional including the gauges, check valves and entire equipment. As far as I am aware at least two firms, and possibly three, specialize in autoclave equipment such as I have employed in the laboratory, and are prepared to furnish equipment of this same kind. Simi- This point is simply made as a precaution in the direcetc.,

propylation was permitted first stage without the addition of alkaline catalys't.

Example 1a The particular autoclave used was one with a capacity of approximately 15 gallons or on theaverage of about pounds of reaction mass. The speed of the stirrer could be varied from to 350 R. P. charge was 11.62

all succeeding steps the pressure never got over about 32 pounds per square inch. In fact, this 11 means that the bulk of the reaction could take place and did take place at an appreciably lower pressure. This comparatively low pressure was the result of the fact that the reactant per se was oxide, and .33 pound of caustic soda were permitted to stay in the autoclave. No additional catalyst was added. Conditions in regard to temperature and pressure were substantially the preceding. In this inbasic. The propylene oxide as added at a rate same as in Example 1a, of about pounds per hour and at a comparastance the oxide was added in '7 hours. The tively moderate temperature, to wit, about 250 amount of oxide added was 43.75 pounds. The 255 F. (moderately higher than the boiling point addition was at the rate of about '7 pounds per of water). The initial introduction of propylene hour. At the end of the reaction period part oxide did not start until the heating devices had 10 of the reaction mass was withdrawn and the reraised the temperature to 245 F. At the commainder of the reaction mass subjected to furpletion of the reaction a sample was taken and ther oxypropylation as described in Example 5a, oxypropylation proceeded as in Example 2a, imimmediately following. mediately following.

Example 5a Example 2a 52.75 pounds of reaction mass identified as 51.97 pounds of the reaction mass identified as Example 4a, preceding, and equivalent to 1.5! Ex pl pr ceding, and equivalent to 6.08 0 pounds of polyamine, 50.86 pounds of propylene p d of the pentamine and 9 pounds of oxide and .10 pound of caustic soda were perpropylene oxide were mixed with .65 pound of mitted to stay in the autoclave. No additional powdered caustic soda as a catalyst and subcatalyst was added. This mass was subjected to lected t0 yal yl n With 2 pounds of propylreaction with 23.50 pounds of propylene oxide. en x Th xyp pyl n w ndu d in The conditions of reaction were substantially the substantially the same manner in regard to temsame as described in Example 1a as far as tempelature and P u e as in Example 1a, precedperature and pressure were concerned. The time ing. Due to the addition of the catalyst and the required to add the oxide was 6 hours. The oxide smaller amount of propylene oxide introduced was added at the rate of about 5 pounds per the time period was much shorter, to wit, 3 hour, hours. The rate of oxide introduction was about In other similar series I have used a catalyst 15 or 16 pounds per hour. At the end of the reat the very beginning, adding some caustic soda action period part of the sample was withdrawn and particularly modestly more than above indiand ox pr py on Co d as in EXample cated; for instance, in a similar experiment I immediately following. added initially 1.15 pounds of caustic soda and continued oxypropylation to give a molecular Example 3a weight range as high as 12,000 to 15,000 and higher with a hydroxyl molecular weight between 56.24 pounds of the reaction mass identified 7,000 to 8,500 or higher. These products so obas Example 2a, preceding, and equivalent to 4.28 10 tained at the higher molecular weight range had pounds of the pentamine, 51.50 pounds of propylthe same characteristics as far as solubility goes, ene oxide and .46 pound of caustic soda were as in Examples 404 and 5a, described in the parapermitted to stay in the autoclave. 16 pounds graph following Table 1. of propylene oxide were introduced in a 4-hour What has been said herein is presented in tabperiod. No additional catalyst was added. The ular form in Table 1 immediately following with conditions of reaction as far as temperature and some added information as to molecular weight pressure were concerned were substantially the and as to solubility of the reaction product in wasame as in Example 1a, preceding. The propylter, xylene and kerosene.

TABLE 1 Composition Before Composition at end M W M I by Hyc l. 1 12;} Time, Amine Oxide Cata- Theo. Amine Oxide Cata- Dc tc1.'- 5F lbs. hrs. Amt., Amt, lyst, M01. Amt, Amt, lyst, mm. sqpm.

lbs. lbs. lbs. Wt. lbs lbs lbs. 11.02 1,000 11.02 07.50 1.25 1, 030 250-255 2537 10 0. 0s 45. so .05 2,410 6.08 72. 89 .05 105 251%255 05-07 3 4.28 51.50 .40 3 110 4.28 07.50 .40 2, 275 250-255 0537 4 a. 12 40.17 .03 5,720 5.12 02.02 .33 a, 575 250-255 05-37 7 5a. 1.71 50.80 .10 10, 900 1. 1 74. 00 .10 0, 300 250255 35-37 0 52.62 pounds of the reaction mass identified as Example 3a, preceding, and equivalent to 3.12 pounds of polyamine, 49.17 pounds of propylene Examples 1a and 2a were both soluble in water and xylene, but insoluble in kerosene; Example 30. was emulsifiable to insoluble in water, soluble in xylene and insoluble in kerosene; Example 4a was insoluble in water, soluble in xylene and dispersible in kerosene; and Example 5a was insoluble in water, but soluble in both xylene and kerosene.

The final product, i. e., at the end of the oxypropylation step, was a somewhat viscous, amber to dark-reddish-amber-colored fluid which was water-insoluble. This is characteristic of all the cue oxide radicals were introduced into the initial initial product is more watermust go to higher molecular weights to produce water-insolubility and kerosene-solubility, for instance, molecular weights such as 12,000 to 15,000 or more on a theoretical basis, and 7,000 to 8,500 or 11,000 on a hydroxyl molecular weight basis. If, however, the initial pentamine compound is treated with one or more or perhaps several moles of butylene oxide then the reverse efiect is obtained and it takes less propylene oxide to produce water-insolubility and kerosene-solubility. These products were, of course, alkaline due in part to the residual caustic soda employed. This would also be the case if sodium methylate were used as a catalyst.

Speaking of insolubility in water or solubility in kerosene such solubility test can be made simply by shaking small amounts of the materials in a test tube with water, for instance, using 1% to 5% approximately based on the amount of water present.

Needless to say, there is no complete conversion of propylene oxide into the desired hydroxylated compounds. This is indicated by the fact that the theoretical molecular weight based on a statistical average is greater than the molecular weight calculated by usual methods on basis of acetyl or hydroxyl value. Actually, there is no completely satisfactory method for determining molecular weights of these types of compounds with a high degree of accuracy when the molecular weights exceed 2,000. In some instances the acetyl value or hydroxyl value serves as satisfactorily as an index to the molecular should be taken which corresponds to the indicated acetyl or hydroxyl value. This matter has been discussed in the literature and is a matter of common knowledge PART 2 acid or anhydride adducts as anhydride, and cyclopenta- Dials-Alder reaction from prod equivalents. polycarboxy atoms.

ated compounds obtained as described in Part 1, preceding, contain nitrogen atoms which may or may not be basic. Thus, it is probable particularly where there is a basic nitrogen atom present that salts may be formed but in any event under conditions described the salt is converted into an ester. This is comparable to similar reactions involving the esterification of triethanolamine. Possibly the addition of an acid such as hydrochloric acid if employed for elimination of the basic catalyst also combines with the basic nitrogen present to form a salt. In any event, however, such procedure does not affect conventional esterification procedure as described herein.

Needless to say, various compounds may be used such as the low molal ester, the anhydride, the acyl chloride, etc. However, for purpose of economy it is customary to use either the acid or the anhydride. A conventional procedure is employed. On a laboratory scale one can employ a resin pot of the kind described in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, and particularly with one more opening to permit the use of a porous spreader if hydrochloric acid gas is to be used as a catalyst.

be present. I have employed hydrochloric acid gas or the aqueous acid itself to eliminate the initial basic material; My preference, however, is to use no catalyst whatsover.

The products obtained in Part 1 preceding may As a general procedure The mixture is shaken to stand overnight. It

acidic solution of the oxypropylated derivatives described in Part 1 is then diluted further with suflicient exylene, decalin, petroleum solvent, or the like, so that one has obtained approximately a 40 solution. To this solution there is added a polycarboxylated reactant as previously described, such as phthalic anhydride, succinic acid or anhydride, diglycollic acid, etc. The mixture is refluxed until esterification is complete as indicated by elimination of water or drop in carboxyl value. Needless to say, if one produces a half-ester from an anhydride such as phthalic anhydride, no water is eliminated. However, if it is obtained from diglycollic acid, for example, water is eliminated. All such procedures are conventional and have been so thoroughly described in the literature that further consideration will be limited to a few examples and a comprehensive table.

Other procedures for eliminating the basic residual catalyst, if any, can be employed. For example, the oxyalkylation can be conducted in absence of a solvent or the solvent removed after oxypropylation. Such oxypropylation end product can then be acidified with just enough concentrated hydrochloric acid to just neutralize the residual basic catalyst. To this product one can then add a small amount of anhydrous sodium sulfate su-fiicient in quantity to take up any water that is present) and then subject the mass to centrifugal force so as to eliminate the hydrated sodium sulfate and probably the sodium chloride formed. The clear somewhat viscous amber-to-dark amber liquid so obtained may contain a small amount of sodium sulfate or sodium chloride but, in any event, is perfectly acceptable for esterification in the manner described.

It is to be pointed out that the products here described are not polyesters in the sense that there is a plurality of both pentamino radicals and acid radicals; the product is characterized by having only one pentamino radical.

In some instances and, in fact, in many instances I have found that in spite of th dehydration methods employed above that a mere trace of water still comes through and that this more trace of water certainly interferes with the acetyl or hydroxyl value determination, at least when a number of conventional procedures are used and may retard esterifica-tion, particularly where there is no sulfonic acid or hydrochloric acid present as a catalyst. Therefore, I have preprocedure. Ihave-ernployed about 200 grams of the polyhydroxylated compound as described in Part 1, preceding; I have added about 60 grams of benzene, and then refluxed this mixture in the glass resin pot using a phase-separating trap until the benzenecarried out all the water present as water'of solution or the equivalent. Ordinarily this refluxing temperature is apt to be in the neighborhood of 130 to possibly 150 C. When all this water or moisture has been removed I also withdraw approximately 20 grams or a little less benzene and then add the required amount-of the carboxy reactant and also about 150 grams of a high boiling aromatic petroleum solvent. These solvents are sold by various oil refineries and, as far assolvent effect act as if they were almost completely aromatic in character. Typical distillation data in the particular type I have employed and found very satisfactory is the following:

I. B. P., 142 C. '50 ml., 242 C. 5 -ml., 200 C. 551111., 244 -C.

50 ml., 248 0. 55 ml., 252 c. '10 m1, 252 C.

10 ml., 209 C. 1-5 ml, 215 C. 20 ml, 216 C.

25 ml., 220 C. 75 1111., 260 C. 30 ml., 225 C. ml., 264 C. 35 ml., 230 C. m1., 270 C. 40 ml., 234 C. m1., 280 C. 45 ml 237 C. ml., 307 C.

After this material is added, refluxing is continued and, of course, is at a higher temperature, to wit, about to C. If the carboxy reactant is an anhydride needless to say no water of reaction appears; if the carboxy reactant is an acid water of reaction should appear and should be eliminated at the above reaction temperature. If it is not eliminated I simply separate out another 10 or 20 cc. of benzene by means of the phase-separating trap and thus raise the temperature to or C., or even to 200 C., if need be. My preference is not to go above 200 C.

The use of such solvent is extremely satisfactory provided one does not attempt to remove the solvent subsequently except by vacuum distillation and provided there is no objection to a little residue. Actually, when these materials are used for a purpose such as demulsification the solvent might just as well be allowed to remain. If the solvent is to be removed by distillation, and particularly vacuum distillation, then the high boiling aromatic petroleum solvent might well be replaced by some more expensive solvent, such as decalin or an alkylated decalin which has a rather definite or close range boiling point. lfhe removal of the solvent, of course, is purely a conventional procedure and requires no elaboration.

In a number of examples, either solvent #7-3 alone was satisfactory, or Xylene alone was satisfactory. This is particularly the case in the instance of higher oxypropylations where the product showed comparatively limited watersolubility, although it sometimes happened that even there it was desirable to mix in a semipolar solvent with xylene; for example, to give a homogeneous system. Note, for example, that xylene was reasonably satisfactory in Examples 13b through 18b, although even here there was some tendency toward turbidity and for this reason in Examples 191) through 30b methanol again was mixed with the xylene in the manner described which was the same procedure employed in Examples I?) through 12b. Thus, in those examples where the mixed solvent was used it shows that two-thirds of the solvent by weight was xylene and one-third by weight was methanol. Xylene was used first by itself. When all the "water had been eliminated methanol equal to one-half the xylene or one-third the subsequent mixture, was added so as to give a single phase system. Other instances have shown that .diethyleneglycol 'diethylether is just as satisfactory, or more satisfactory, than methanol, or a mixture of these 'two semi-polar solvents can be used.

Another obvious procedure, of course, is to merely distill off a solvent such as xylene or solvent Z-3 and then dissolve the product in a semi-polar solvent, such as methanol, ethanol, propanol, etc. It is purely a matter of convenience to employ first a non-polar solvent (water-insoluble to eliminate the water during distillation) and then add a suitable polar solvent (hydrophile) to give a single-phase system.

TKBIZET 2:

A m'tj. of Ex. No. Ex. No. 3- of Acid of arboxy Ester H. O. Reaetant 80'. 73 58-.-0 175' 87.5- 175 itracon 6826' 175 630 .Aconitic Acid; 107 116 ,105 Dialycoli'A'cid. 6124 116' 134 2, 105v Oxalic Acid. u 60. 6 116 134. 2,-105. Maleic Anhydride 44. 5 116 134 23105 Phthalic Anhydrid 70. 4 116 134 2;105; .Citraconlc Anhydride. 50. 2 116 134v 2, 105 Aconitic Acid" 81. 90.1 123 2;275 Diglycolic Acid I 59. 0 90.1 123* 2275 -Oxalic Aci L 54.8.; 90.1. 123 2, 275. .Maleic Anhydride. 41. 31 90:1 123 2, 275' Phthali'c Anhydride 60. 6* 90.1 123 2, 275 .Citraconic-Anhydride; 48. 5; 90. l 123 2, 275 Acunitic Acid: 72. 49' 78. 5 3.575 DiglycolicAcid 365 49 7825 3,575 Oxalic Acid 34.5 49. 78. 5 v 3, 575- 28.5 49' 78. '5' 3, 575 thalic Anhydnde... 43.9 49 78. 5 3,:575 Oitraconic Anhydride- 30. 0 49 78. 5 3, 575 AconiticjA'cidj 45.8 25. 8 44. 5 6, 300- Di flyco'lic Acid 21. 6 25. 8 44. 5 6, 300' "in A V 21. 1 s 8. 44. 5 6, 300. Male-1c 'Auhydride 15.8 25.8 4415 6; 300 Phthah'e A'nhydr'ide; 26.5 25. 8 44. 5 6, 300 Oitraconic Anhydlide.- 18.3 8 44. 5 6, 300 Aconitic Acid; 27. 1

eliminated, at. least: for: exploration experimolecule; increases and. the: reactive hydroxyl radical represents'saasmallezz fraction :of the entire :molecule; more? difficulty isrinvolvedtin obtaining; complete. esterification.v

Even-underithexmost carefully controlled con-'- T DI C I manufacturing the esters boxylicrrea'ctant which can be removed" by filas ,been, illustrated by preceding examplesw If 0 tration'or, if'desired; the esterification procedure forany reason reaction does not take place m canJoe-repeatedusing-anappropriately-reamed mannenihat-yis acceptable, attentionshould be ratio ofearboxylic reaetant.- directedto the following detailss. (aiRecheck Even-the-determjnation ofJthehydroxyl'vaIue equivalent amount of acid; (b) if the-reaction lviouslytreferred t orrforthat-.ma,tter .the pres, does not proceed With= reasonablepspeedeither ence of anytinorganicsalts or--propylene'oxide. raise the temperature indicated orelse-extend the Obviously this oxide shouldbeeliminated:

period of time, up to .12 or 16 hours :if need=be-;- The. solvent employed; if-any; can-be removed (0) if necessary, use of paratoluene sulfonic from the finished ester .by distillation and par-- organic. salt such. as sodium chloride-tor sodium chars-and-the'likea Howevenfor-the-purpose of sulfate is not precipitatinggout. Such salt should be 19 demulsiflcation or the like color is not a factor and decolorization is not justified.

In the above instance I have permitted the solvents to remain present in the final reaction mass. In other instances Ihave followed the same procedure using decalin or a mixture of decalin or benzene in the same manner and ultimately removed all the solvents by vacuum distillation. Appearance of the final products are much the same as the diols before'esterification and in some instances were somewhat darker in color and had a reddish cast and perhaps somewhat more viscous.

PART 3 In the hereto appended claims the demulsifying agent is described as an ester obtained from a polyhydroxylated material prepared from a pentamine. If one were concerned with a monohydroxylated material or a dihydroxylated material one might be able to write a formula which particular product. However, in a more highly hydroxylated material the problem becomes difficult for reasons which have already been indicated in connection with oxypropylation and which can be examined by merely considering for the moment a monohydroxylated material.

Oxypropylation involves the same sort of variations as appear in preparing high molal polypropylene glycols. Propylene glycol has a secondary alcoholic radical and a primary alcohol radical. Obviously then polypropylene glycols could be obtained, at least theoretically, in which two secondary alcoholic groups are united or a secondunited to a primary alcohol group, etherization being involved, of course, in each instance. Needless to say, the same situation applies when one has oxypropylated polyhydric materials having 4 or more hydroxyls, or the obvious equivalent.

Usually no effort is made to differentiate between oxypropylation taking place, for example, at the primary alcohol radical or the secondary alcohol radical. Actually, when such products are obtained, such as a high molal polypropylene glycol or the products obtained in the manner herein described one does not obtain a single derivative such as HO(R O)nI-I or -(RO)1rH in which n has one and only one value, for instance, 14, or 16, or the like. Rather, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by any known procedure without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture. On a statistical basis, of course, n can be appropriately specified. For practical purposes one need only consider the oxypropylation of a monohydric alcohol because in essence this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant one cannot draw a single formula and say that by following such procedure one can readily obtain 80% or 90% or 100% of such compound. However, in the case of at least monohydric in'tial reactants one can readily draw the formulas of a large number of compounds which appear in some of the probable mixtures or can be prepared as components and mixtures which are manufactured conventionally.

Simply by way of illustration reference is made 20 to the copending application of De Groote, Wirtel, and Pettingill, serial No. 109,791, filed August 11, 1949 (now Patent 2,549,434, granted April 17, 1951).

However, momentarily referring again to a monohydric initial reactant it is obvious that if one selects any such simple hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylations, or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxide except for the This is particularly true where comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which, for the sake of convenience, may be indicated as RO(C2H4O)30OH. Instead, one obtains a cogeneric mixture of closely related homologues, in which the formula may be shown as the following, RO(CzI-I4O)1LH, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where n may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difficulty, it is necessary to resort to some other method of description, or else consider the value of n, in formulas such as those which have appeared previously and which appear in the claims, as representing both individual constituents in which n has a single definite value, and also with the understanding that n represents the average statistical value based on the assumption of completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of propylene oxide per hydroxyl is 15 to 1. In a generic formula 15 to 1 could be 10, 20, or some other amount and indicated by n. Referring to this specific case actually one obtains products in which n probably varies from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula is best described also in terms of method of manufacture.

The significant fact in regard to the oxypropylated polyamines herein described is that in the initial stage they are substantially all water-soluble, for instance, up to a molecular weight of 2,500 or thereabouts. Actually, such molecular weight represents a mixture of some higher molecular weight materials and some lower molecular weight materials. The higher ones are probably water-insoluble. The product may tend to emulsify or disperse somewhat because some of the constituents, being a cogeneric mixture, are water-soluble but the bulk are insoluble. Thus one gets emulsifiability or dispersibility as noted. Such products are invariably xylenesoluble regardless of whether the original reactants were or not. Reference is made to what has been said previously in regard to kerosenesolubility. For example, when the theoretical molecular weight gets somewhere past 4,000 or at approximately 5,000 the product is kerosenesoluble and water-insoluble. These kerosenesoluble oxyalkylation products are most desirable for preparing the esters. I have prepared hydroxylated compounds not only up to the theoretical molecular weight shown previously, 1. e., about 11,000 but some which were much higher. I have prepared them, not only from the polyamine here described, but also from oxyethylated or oxybutylated derivatives previously referred to. The exact composition is open to question for reasons which are common to all oxyalkylation. It is interesting to note, however, that the molecular weights based on hydroxyl determinations at this point were considerably less, in the neighborhood of a third or a fourth of the value at maximum point. Referring again to previous data it is to be noted, however, that over the range shown of kerosenesolubility the hydroxyl molecular weight has invariably stayed at two-thirds or five-eighths of the theoretical molecular weight.

It becomes obvious when carboxylic esters are prepared from such high molecular weight materials that the ultimate esterification product again must be a cogenerio mixture. Likewise, it is obvious that the contribution to the total molecular weight made by the polycarboxy acid is small. By the same token one would expect the effectiveness of the demulsifier to be comparable to the unesterified hydroxylated material. Remarkably enough, in many instances the prodnot is distinctly better.

PART 4 As pointed out previously the final product obtained is a fractional ester having free carboxyl radicals. Such product can be used as an intermediate for conversion into other derivatives which are eiTective for various purposes, such as the breaking of petroleum emulsions of the kind herein described. For instance, such product can zyl alcohol, octadecyl alcohol, etc. ucts are aso valuable for a variety of purposes due to their modified solubility. This is particularly true where surface-active materials are of value and especially in demulsification of waterin-oil emulsions.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

l. A hydrophile synthetic product which is the ester of (A) a polycarboxy acid with (B) a high molal oxypropylated monomeric pentamino 2500 to 30,000 on an average statistical basis; ((2) the ratio of propylene oxide per initial reactive hydrogen atom of the monomeric pentamino compound be within the range of 7 to 70; (e) the monomeric pentamino compound represent not more than 20% by weight of the oxypropylated monomeric pentamino compound on a statistical basis; (1) the preceding provisos being based on the assumption of complete reaction between the propylene oxide and the monomeric pentamino compound; (9) the nitrogen atoms are linked by ethylene radicals; (h) the ratio of polycarboxy acid to oxypropylated monomeric pentamino compound being one mole of the former for each reactive hydrogen atom of the latter; and (i) the polycarboxy acid be selected from the group consisting of acyclic and isocyclic dicarboxy and tricarboxy acids composed of carbon, hydrogen and oxygen and having not more than 8 carbon atoms.

2. A product as in claim 1 in which at least one of the nitrogen atoms of the oxypropylated monomeric pentamino compound is basic.

3. A product as in claim 1 in which at least.

two nitrogen atoms of the oxypropylated monomeric pentamino compound are basic.

4. A product as in claim 3 in which the polycarboxy acid is a dicarboxy acid.

5. A product as in claim 4 in which the monomeric pentamino compound is tetraethylenepentamino.

6. The product of claim 1 wherein the dicarboxy acid is diglycollic acid.

7. The product of claim 1 wherein the dicarboxy acid is maleic acid.

8. The product of claim 1 wherein the dicarboxy acid is phthalic acid.

9. The product of claim 1 wherein the dicarboxy acid is citraoonic acid.

10. The product of claim 1 wherein the dicarboxy acid is succinic acid.

No references cited.

Such prod- 

1. A HYDROPHILE SYNTHETIC PRODUCT WHICH IS THE ESTER OF (A) A POLYCARBOXY ACID WITH (B) A HIGH MOLAL OXYPROPYLATED MONOMERIC PENTAMINO COMPOUND WITH THE PROVISO THAT (A) THE MONOMERIC PENTAMINO COMPOUND BE FREE FROM ANY RADICAL HAVING AT LEAST 8 UNINTERRUPTED CARBON ATOMS AND BE COMPOSED OF ELEMENTS SELECTED FROM THE GROUP CONSISTING OF CARBON, HYDROGEN, OXYGEN AND NITROGEN; (B) THE MONOMERIC PENTAMINO COMPOUND HAVE A MOLECULAR WEIGHT OF NOT OVER 800 AND AT LEAST A PLURALITY OF REACTIVE HYDROGEN ATOMS; (C) THE OXYPROPYLATED MONOMERIC PENTAMINO COMPOUND HAVE A MOLECULAR WEIGHT OF 2500 TO 30.000 ON AN AVERAGE STATISTICAL BASIS; (D) THE RATIO OF PROPYLENE OXIDE PER INITIAL REACTIVE HYDROGEN ATOM OF THE MONOMERIC PENTAMINO COMPOUND BE WITHIN THE RANGE OF 7 TO 70; (E) THE MONOMERIC PENTAMINO COMPOUND REPRESENT NOT MORE THAN 20% BY WEIGHT OF THE OXYPROPYLATED MONOMERIC PENTAMINO COMPOUND ON A STATISTICAL BASIS; (F) THE PRECEDING PROVISOS BEING BASED ON THE ASSUMPTION OF COMPLETE REACTION BETWEEN THE PROPYLENE OXIDE AND THE MONOMERIC PENTAMINO COMPOUND; (G) THE NITROGEN ATOMS ARE LINKED BY ETHYLENE RADICALS; (H) THE RATIO OF POLYCARBOXY ACID TO OXYPROPYLATED MONOMERIC PENTAMINO COMPOUND BEING ONE MOLE OF THE FORMER FOR EACH REACTIVE HYDROGEN ATOM OF THE LATTER; AND (I) THE POLYCARBOXY ACIDS BE SELECTED FROM THE GROUP CONSISTING OF ACYCLIC AND ISOCYCLIC DICARBOXY AND TRICARBOXY ACIDS COMPOSED OF CARBON, HYDROGEN AND OXYGEN AND HAVING NOT MORE THAN 8 CARBON ATOMS. 